EP3245194A1 - Facile method for preparation of sodium 5-nitrotetrazolate using a flow system - Google Patents
Facile method for preparation of sodium 5-nitrotetrazolate using a flow systemInfo
- Publication number
- EP3245194A1 EP3245194A1 EP16704094.8A EP16704094A EP3245194A1 EP 3245194 A1 EP3245194 A1 EP 3245194A1 EP 16704094 A EP16704094 A EP 16704094A EP 3245194 A1 EP3245194 A1 EP 3245194A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- approximately
- acid
- flow system
- reaction
- continuous flow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
- C07D257/06—Five-membered rings with nitrogen atoms directly attached to the ring carbon atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
Definitions
- the present invention is directed to the field of substituted tetrazole synthesis and manufacture. More particularly, the present invention is directed to processes for preparing substituted tetrazoles and tetrazolate salts, such as sodium 5-nitrotetrazolate, utilizing flow chemistry techniques. The use of the present technique results in less hazardous, more efficient large scale manufacturing processes.
- NaNT Sodium 5-nitrotetrazolate
- NaNT is synthesized via a Sandmeyer type reaction that involves displacement of a diazonium group by a nucleophile, in this case nitrite ion resulting in a nitro group, in the presence of cupric salts.
- a nucleophile in this case nitrite ion resulting in a nitro group
- This procedure involves addition of a solution of commercially available 5-aminotetrazole ("5-AT,” 1) in aqueous nitric acid to a solution of copper(II) sulfate and sodium nitrite to generate the diazonium ion (3), which undergoes substitution to afford the acid copper salt of 5-nitrotetrazole ("5 -NT," 5).
- the reaction temperature must be tightly controlled at or below 18°C due to the thermal instability of the diazonium intermediate.
- the second process step utilizes aqueous sodium hydroxide to convert the acid copper salt of 5-NT into NaNT and generates copper oxide as a byproduct.
- micro-detonations which occur if the mixing of the 5-AT and sodium nitrite solutions is not tightly controlled. These micro-detonations may be caused by nitrogen oxide fumes from the reaction solution reacting with droplets of 5-AT on surfaces in the reactor to form 5- diazotetrazole (4), which may spontaneously detonate in solution when the concentration exceeds 1%.
- Fronabarger also describes an alternate method for producing NaNT utilizing microreactor technology, which does not use copper to stabilize the tetrazole diazonium intermediate and which involves direct reaction of 5-AT/nitric acid with sodium nitrite at ambient temperature in a continuous flow regime. Unlike a batch process, this procedure generates only very small amounts of the unstable reaction intermediates in a dilute media, which are subsequently consumed via substitution as a part of the flow process. This process provides a safe method for preparation of 5-nitrotetrazolates, as only minor amounts of the intermediates are generated per unit time and accumulation is not possible, but requires extensive time and an appropriate microreactor system optimized for 5-NT production for the flow process.
- U. S. Publication No. 2014/0206885 also describes a continuous flow process for production of 5-nitrotetrazolates, which does not use copper to stabilize the diazonium intermediate reactant and involves direct reaction of 5-AT/nitric acid with sodium nitrite at an elevated reaction temperature to promote expedient substitution of the nitro group in place of the diazo group and to ensure rapid consumption of hazardous reactants.
- the diazonium intermediate becomes unstable at higher reaction temperatures, instead of being quickly converted into the desired 5-NT, the diazonium intermediate may in certain infrequent cases instead form minor amounts of 5-azidotetrazole, which is a highly explosive and undesirable side product. As a result, the final product may have an undesirable purity profile and additional purification steps may be required.
- a method for preparing salts of 5-nitrotetrazolate comprises reacting aqueous solutions of 5-aminotetrazole, an acid, and sodium nitrite in a continuous flow system at ambient temperature, which in some embodiments may be in a range of approximately 10°C to approximately 50°C, or may be in a range of approximately 20°C to approximately 30°C.
- the sodium nitrite is added in excess to control pH within a pH range of approximately 4 to approximately 5.
- the acid may comprise nitric acid, sulfuric acid, or perchloric acid.
- the 5-aminotetrazole and the acid may comprise one reactant stream, and the sodium nitrite may comprise a second reactant stream.
- the continuous flow system may further comprise a processing zone that is held at the ambient temperature.
- the processing zone may comprise a mixing zone that combines the first reactant stream and the second reactant stream into a reactant mixture and a reaction zone that is configured to retain the reactant mixture in the reaction zone until the reaction is complete.
- the reaction zone retains the reactant mixture in the processing zone until a product with at least 60% yield of sodium 5-nitrotetrazolate is achieved.
- the product may be produced at a rate of at least 100 g/hour.
- a reaction product of 5-aminotetrazole, an acid, and sodium nitrite is prepared via a continuous flow system at ambient temperature, wherein the reaction product comprises at least 60% yield of sodium 5- nitrotetrazolate.
- a continuous flow system for preparing salts of 5-nitrotetrazolate comprises a first reactant stream comprising 5- aminotetrazole and an acid, and a second reactant stream comprising sodium nitrite, a mixing zone that combines the first reactant stream and the second reactant stream into a reactant mixture, and a reaction zone that is configured to retain the reactant mixture at a constant temperature until the reaction is complete.
- the acid may comprise nitric acid, sulfuric acid, or perchloric acid.
- the mixing zone and the reaction zone may be held at the ambient temperature in a range of approximately 10°C to approximately 50°C, or may be held at the ambient temperature in a range of approximately 20°C to approximately 30°C.
- the reaction zone may retain the reactant mixture until a product with at least 60% yield of sodium 5- nitrotetrazolate is achieved.
- a method for preparing a salt of 5-nitrotetrazolate comprises (a) mixing an aqueous solution of 5- aminotetrazole and an acid with an aqueous solution of a nitrite salt in a continuous flow system to form a reactant mixture, (b) retaining the reactant mixture in a processing zone of the continuous flow system at a constant temperature, (c) forming an aqueous product within the reaction zone, and (d) collecting the aqueous product.
- the constant temperature may be in a range of approximately 10°C to approximately 50°C, or may be in a range of approximately 20°C to approximately 30°C.
- Figure 1 is a depiction of certain intermediates formed during preparation of
- Figure 2 is a flow diagram of a method used for preparation of NaNT, according to certain embodiments of the present invention.
- Figure 3 is a flow diagram of a method used for preparation of NaNT, according to certain embodiments of the present invention.
- Figure 4 is a depiction of a method used for preparation of NaNT, according to certain embodiments of the present invention.
- NaNT is prepared utilizing a continuous flow system 10, such as the embodiments illustrated in Figures 2 and 3.
- NaNT may be prepared by reacting aqueous solutions of 5-AT, a suitable acid such as nitric, sulfuric or perchloric acid, and sodium nitrite in the continuous flow system 10. The components may be reacted under conditions suitable to synthesize a high purity, concentrated aqueous solution of NaNT.
- the components may be introduced into the continuous flow system 10 by mixing water, 5-AT, and an appropriate acid to form a first reactant stream 12, and adding an aqueous solution of an appropriate nitrite as a second reactant stream 14.
- each reactant may be separately introduced into the continuous flow system 10.
- the acid may be selected from any known acid or mixture of acids that will, when mixed with 5-AT and a nitrite, facilitate substitution of the nitro group in place of the diazo group in the diazonium intermediate.
- Most strong inorganic acids are suitable for use in the present invention. Non-limiting examples would include nitric, sulfuric, or perchloric acids.
- the nitrite may be selected from any known nitrite or mixture of nitrites that will, when mixed with 5-AT and an acid, facilitate substitution of the nitro group in place of the diazo group in the diazonium intermediate. Non-limiting examples may include sodium, potassium, or lithium nitrites.
- one or more pumps 16 may be used to transport the reactant steams 12, 14 from storage tanks or vessels into the continuous flow system 10. In the current invention, peristaltic pumps are used to maintain the high flow rates required.
- the processing zone 18 may comprise a mixing zone 24 and/or a reaction zone 28.
- the processing zone 18 may be designed so that the reaction may be carried out in the processing zone 18 with an ambient temperature in a range of approximately 10°C to approximately 50°C. Alternatively, the reaction may be performed in the processing zone 18 with an ambient temperature in a range of approximately 20°C to approximately 30°C.
- the diazonium intermediate remains stable so as to minimize side reactions that may produce hazardous and undesirable impurities in the final product. While the ambient reaction temperature may be helpful to minimize unstable side reactions of the diazonium ion, the ambient reaction temperature may also decrease the rate of substitution of nitro groups in place of the diazo groups on the diazonium ion, thus leaving an undesirable (albeit stable) impurity concentration of diazonium ions in the final product.
- Other process variables may be adjusted or controlled in order to compensate for a potentially diminished rate of substitution at the ambient reaction temperature.
- another option to achieve the desired substitution rate may be to maintain the pH of the reactant mixture 26 within a predetermined range, such as within a pH range of approximately 4 to approximately 5.
- Other pH ranges may be considered and not limited by the current invention; however, reacting outside of the claimed pH range will likely result in an altered impurity profile.
- Controlling the pH within the desired range is conventionally done through incorporation an additional buffering agent, which is often selected from among suitable phosphates and acetates. These buffering agents are typically chosen so that they will not to participate as a reactant in the reaction. As a result, an additional filtration or purification step is typically needed to remove the buffering agent from the final product.
- one or more of the reactants may be added at a concentration level that allows the reactant to both effect the substitution reaction to provide the desired purity and concentration of 5-nitrotetrazolate, as well as to act as a buffering agent to maintain the pH within the desired range.
- the nitrite may be supplied to the continuous flow system 10 in an amount sufficient to react with the acid to generate a diazonium intermediate from the 5- AT and provide sufficient excess nitrite to form 5 -NT, as well as to control the pH of the reactant mixture 26 within a range of approximately 4 to approximately 5.
- the nitrite may be supplied to the continuous flow system 10 in a molar ratio of at least 2 moles of nitrite per mole of 5- AT, up to 10 moles of nitrite per mole of 5 -AT, or even greater ratios of moles of nitrite to moles of 5- AT.
- the acid may be supplied to the continuous flow system 10 in an amount sufficient to react with the nitrite to generate a diazonium intermediate from the 5-AT and provide a 5-NT.
- the acid may also be supplied in an amount sufficient to control the pH of the reactant mixture 26 within a range of approximately 4 to approximately 5.
- the acid may be supplied to the continuous flow system 10 in a molar ratio of at least 2 moles of protons per mole of 5-AT, up to 10 moles of protons per mole of 5-AT, or even greater ratios of moles of protons to moles of 5-AT.
- all of the components of the processing zone 18 may be heated or cooled by a common heat source, such as a common water bath, oven, heat exchanger, or other heat source/sink.
- a common heat source such as a common water bath, oven, heat exchanger, or other heat source/sink.
- different heat sources/sinks may be used among the mixing zone 24 and reaction zone 28 as needed and/or desired to achieve different temperatures within each area in order to further optimize the reaction within the continuous flow system 10.
- the first reactant stream 12 may pass into the continuous flow system 10 and the second reactant stream 14 may pass into the continuous flow system 10 prior to being combined in the mixing zone 24.
- the mixing zone 24 may be a mixing T. It is contemplated that mixing of the reactants may be performed using any type of device that would allow continuous blending or merging of the reactant streams 12, 14, including but not limited to a transfer pump, a static mixer, an oscillatory baffled reactor, a mechanical agitator, and/or a continuously stirred tank reactor. Alternatively, it is contemplated that a series of mixing devices may be used to introduce the reactants gradually via a manifold.
- the reaction zone 28 may comprise a reaction coil of sufficient length and volume to provide a retention time in the processing zone 18 until the reaction is complete. More specifically, the reaction zone 28 may be configured to allow the reaction to proceed within the processing zone 18 until a product with at least 60% yield of NaNT is achieved, which may further range up to a 95% yield of NaNT.
- the combination of reactants Upon mixing, the combination of reactants generates large volumes of gas as a result of substitution of the diazonium species. As illustrated in Figure 3, this gas may optionally be released using a gas/liquid separator 30 either inside or outside the processing zone 18 or, as illustrated in Figure 2, may be confined in the flow tubing until it exits the flow reactor. The product then exits the processing zone 18, where it is collected in a suitable vessel.
- the excess nitrite is still present in the reactant mixture 26 after the substitution reaction has reached completion.
- additional acid may be added to the reactant mixture 26 at any one or more of various suitable locations, which include but are not limited to a late stage of the reaction zone 28 at a point where the reaction is nearing or at completion; at the point where the reactant mixture 26 exits the processing zone 18; and/or after the reactant mixture 26 is being held the receiving vessel.
- the excess nitrite and acid forms N2O3, which then bubbles out of the reactant mixture 26, thus removing the excess nitrite as a potential impurity in the final product.
- the manufacturing process depicted in Figures 2 and 3 may be carried out, either in whole or in part, in a flow system.
- the flow system may be comprised of tubing of a composition suitable for containing the reactants at the prescribed temperatures. Additionally, the tubing may be of any diameter that allows for flow rates and retention times that provide for the rapid conversion of 5-AT to 5 -NT.
- the pumping devices 16 will supply the reactants at a flow rate that allows for continuous mixing as well as a system retention time that allows for complete reaction in the processing zone 18.
- performance of the process at ambient temperature and use of excess nitrite for pH control within a range that increases the rate of the substitution reaction produces an aqueous product that comprises highly concentrated NaNT with minimal impurities, and which can be produced in greater quantities than are possible prior art methods.
- the rate of production of product with these characteristics is at least 100 g/hour. It should be noted though, that a critical attribute of this invention is that this process is scalable to whatever production rates are necessary.
- Tables I, II, and III list the impurity contents for NaNT produced from both prior art and the inventive method described in this application.
- Sample EL4C153-120 listed in Table I was produced using the method outlined in U.S. Publication No. 2014/0206885.
- Sample EL4M123B listed in Table II was produced using the method described in this application.
- Samples 73387, 73272, 72756, 72757, and 73213 were produced using a Batch-Sandmeyer Process, and Samples 4M123B and 4M125B were produced using the method described in this application.
- the present method reaction product comprises at least 60% yield of sodium 5-nitrotetrazolate and with only minor amounts of other impurities as shown in Tables II and III.
- the solution was treated with a 10% by volume of 11.7 M perchloric acid to remove excess nitrite from the solution.
- a 10% by volume of 11.7 M perchloric acid As an example, approximately 7,750 mL of product was treated with 750mL of 11.7 M perchloric acid, yielding a final volume of 8,500 mL.
- HPLC analysis of the reaction mixture indicated sodium 5- nitrotetrazolate with a concentration of 0.115 grams of NaNT per milliliter of solution, which corresponds to a yield of 73% based on 5-AT.
- BNCP Tetraammine-cis-bis[5-nitro-2H-tetrazolato-N 2 ] cobalt (III) perchlorate
- the length of the tubing from the pumps 16 into the mixing T 24 was 2.5 feet and was 10.8 feet (331cm) after the mixing T 24 and connected into a 2nd reaction zone of tubing consisting of tubing diameter of 0.250 inches (6.35 mm) (ID) and a length of 10.3 feet (315 cm).
- This configuration provided a retention time of approximately 25 minutes in the processing zone 18 and a post mixing volume of approximately 500mL.
- the processing zone 18 (in this case a water bath) was maintained at 20-25°C during operation.
- the continuous flow system 10 was allowed to come to equilibrium for approximately 25 minutes before product was acquired.
- the resulting concentrations of the solution constituents are as follows; NaNT: 0.054 grams/mL; nitrate ion: 0.046 grams/mL; IH-tetrazole: 0.003 grams/mL; nitrite ion: 0.004grams/mL; and 5-azidotetrazole: below the equipment's detection limit of 325 ppm.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201562104240P | 2015-01-16 | 2015-01-16 | |
PCT/US2016/013858 WO2016115564A1 (en) | 2015-01-16 | 2016-01-19 | Facile method for preparation of sodium 5-nitrotetrazolate using a flow system |
Publications (2)
Publication Number | Publication Date |
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EP3245194A1 true EP3245194A1 (en) | 2017-11-22 |
EP3245194B1 EP3245194B1 (en) | 2019-05-01 |
Family
ID=55349956
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP16704094.8A Active EP3245194B1 (en) | 2015-01-16 | 2016-01-19 | Process and contiuous flow system for prearing sodium 5-nitrotetrazole at a rate of at least 100 gram/hour and at a temperature of 10-30 °c |
Country Status (4)
Country | Link |
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US (1) | US9718791B2 (en) |
EP (1) | EP3245194B1 (en) |
ES (1) | ES2736874T3 (en) |
WO (1) | WO2016115564A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP3510020B1 (en) | 2016-09-07 | 2020-12-16 | Pacific Scientific Energetic Materials Company | Purification of flow sodium 5- nitrotetrazolate solutions with copper modified cation exchange resin |
US10947204B1 (en) | 2019-10-17 | 2021-03-16 | U.S. Government As Represented By The Secretary Of The Army | Method for preparing sodium nitrotetrazolate using cation exchange resin |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2066954A (en) | 1931-07-10 | 1937-01-05 | Herz Edmund Von | C-nitrotetrazole compounds |
US3054800A (en) | 1949-09-17 | 1962-09-18 | Harry P Burchfield | 3, 5-dinitro-1, 2, 4-triazoles and process for preparing same |
US3111524A (en) | 1957-05-06 | 1963-11-19 | Richard H Wiley | Preparation of 3, 5-dinitro-1, 2, 4-triazole |
GB1519796A (en) | 1975-11-11 | 1978-08-02 | Secr Defence | Production of 5-nitotetrazole salts |
US4093623A (en) | 1977-05-05 | 1978-06-06 | The United States Of America As Represented By The Secretary Of The Navy | Method of preparing the acid copper salt of 5-nitrotetrazole |
US4552598A (en) | 1984-05-17 | 1985-11-12 | The United States Of America As Represented By The United States Department Of Energy | Ethylenediamine salt of 5-nitrotetrazole and preparation |
US6375871B1 (en) | 1998-06-18 | 2002-04-23 | 3M Innovative Properties Company | Methods of manufacturing microfluidic articles |
US6167910B1 (en) | 1998-01-20 | 2001-01-02 | Caliper Technologies Corp. | Multi-layer microfluidic devices |
US6749814B1 (en) | 1999-03-03 | 2004-06-15 | Symyx Technologies, Inc. | Chemical processing microsystems comprising parallel flow microreactors and methods for using same |
DE19949551C2 (en) | 1999-10-14 | 2001-12-13 | Agilent Technologies Inc | Microfluidic microchip, energy supply device and method for operating a microfluidic microchip |
WO2001059013A1 (en) | 2000-02-09 | 2001-08-16 | Clariant International Ltd | Method for production of azo dyes in microreactors |
DE10032019A1 (en) | 2000-07-01 | 2002-01-10 | Clariant Gmbh | Process for the preparation of disazo condensation pigments in microreactors |
GB0126281D0 (en) | 2001-11-01 | 2002-01-02 | Astrazeneca Ab | A chemical reactor |
WO2006029193A2 (en) | 2004-09-08 | 2006-03-16 | Pacific Scientific Energetic Materials Company | Process for preparing substituted tetrazoles from aminotetrazole |
CA2897068C (en) | 2013-01-22 | 2019-09-03 | Pacific Scientific Energetic Materials Company | Facile method for preparation of 5-nitrotetrazolates using a flow system |
US9598380B2 (en) | 2014-06-12 | 2017-03-21 | Sri International | Facile method for preparation of 5-nitrotetrazolates using a batch system |
-
2016
- 2016-01-19 US US15/000,444 patent/US9718791B2/en active Active
- 2016-01-19 ES ES16704094T patent/ES2736874T3/en active Active
- 2016-01-19 WO PCT/US2016/013858 patent/WO2016115564A1/en active Application Filing
- 2016-01-19 EP EP16704094.8A patent/EP3245194B1/en active Active
Also Published As
Publication number | Publication date |
---|---|
US9718791B2 (en) | 2017-08-01 |
US20160207892A1 (en) | 2016-07-21 |
EP3245194B1 (en) | 2019-05-01 |
ES2736874T3 (en) | 2020-01-08 |
WO2016115564A1 (en) | 2016-07-21 |
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